Asymmetric Propargylic Radical Cyanation Enabled by Dual Organophotoredox and Copper Catalysis

• DOI: 10.1021/jacs.9b02338
• Publication Date: 2019-03-31T17:51:21Z
• Authors: Fu-Dong Lu; Dan Liu; Lei Zhu; Liang-Qiu Lu; Qian Yang; Quan-Quan Zhou; Yi Wei; Yu Lan; Wen-Jing Xiao
• Keywords: 01 natural sciences; 0104 chemical sciences

The first asymmetric propargylic radical cyanation was realized through a dual photoredox and copper catalysis. An organic photocatalyst serves to both generate propargyl radicals and oxidize Cu(I) species to Cu(II) species. A chiral Cu complex functions as an efficient organometallic catalyst to resemble the propargyl radical and cyanide in an enantio-controlled manner. Thus, a diverse range of optically active propargyl cyanides were produced with high reaction efficiency and enantioselectivities (28 examples, 57-97% yields and 83-98% ee). Moreover, mechanistic investigations including experiments and density functional theory calculations were performed to illustrate on the reaction pathway and stereochemical results.